Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/12—Polymerisation in non-solvents
  • C08F2/16—Aqueous medium
  • C08F2/22—Emulsion polymerisation
  • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
  • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic

Definitions

• This invention relates to the use of a fatty oil ex Helianthus annuus for the preparation of emulsifiers for emulsion polymerization.
• alkali metal salts of fatty acids are particularly suitable for the emulsion polymerization of monomers, such as butadiene, styrene, chloroprene or acrylonitrile; cf. R. R. Dunbrook, India Rubber Wld. 117, 203 (1948). Stable latices are formed and may readily be coagulated by acidification or with a saturated sodium chloride solution. It has been shown that, compared with one another, the salts of C 16 -C 18 fatty acids used as emulsifiers in the copolymerization of butadiene give the same polymerization velocities of the monomers (H.
• Unsaturated fatty acids are distinguished from saturated fatty acids having the same number of carbon atoms by their liquid consistency and by the better solubility of their alkali metal salts. This provides for better handling in practice.
• sodium oleate has already played a significant role in the development of the emulsion polymerization of synthetic rubber. It is an effective emulsifier, even at low temperatures (M. H. Reich, B. Moss, J. M. Gyenge, Rubber Age (N.Y.) 76, page 391 (1954)).
• liquid and solid fatty acids can be separated by
• fatty acids of high oleic acid content are available from the hoofs of slaughtered cattle (neat's-foot oil, 79% oleic acid), although in this case, too, separation with wetting agents or an extraction process is normally carried out to free the oleic acid from around 20% saturated fatty acids.
• tall oil has been used as a raw material for emulsifiers for emulsion polymerization.
• the abietic acid content of tall oil makes a catalytic hardening process (disproportionation) absolutely essential, cf. German patent 2,510,803.
• the present invention is based on the surprising observation that a fatty oil ex Helianthus annuus (sunflower) of a species known, for example, from U.S. Pat. No. 4,627,192, which is expressly incorporated herein by reference, which has an oleic acid content of 78 to 92% by weight, more especially 84 to 90% by weight, and a linoleic acid content of 2 to 10% by weight and more especially 6 to 8% by weight, is eminently suitable despite its high linoleic acid content for the production of alkali metal, ammonium and/or alkanolammonium salts of optionally dihydroxy-substituted fatty acids as emulsifiers for emulsion polymerization without any need for enrichment processes, such as pressing, extraction or wetting agent separation processes.
• the sunflower species and lines from which the fatty oils used herein are derived include SIGCO 41A, SIGCO 41B, SIGCO 4117B, SIGCO 416R, SIGCO 853R, SIGCO 273W, and sunflower lines based on the foregoing.
• fatty oils used as starting materials are natural substances, the proportions of their principal components are subjected to certain variations.
• the fatty oils typically show the following ranges of variation with respect to the fatty acids:
• erucic acid up to 1% by weight of one or more of the following acids: myristic, palmitoleic, linolenic, arachic, eicosenoic, and erucic acid.
• the fatty acids can be directly obtained by splitting, for example pressure splitting, of the fatty oil, for which purpose simple distillation is sufficient.
• the fatty acids thus obtained are then directly converted into the alkali metal, ammonium, or alkanolammonium (e.g. mono-, di-, or triethanolammonium) salts, more especially sodium and potassium salts.
• oleic acids may also be converted by epoxidation and hydrolysis of the epoxide bond with water into so-called dihydrostearic acids which in turn are eminently suitable as emulsifiers for the production of polyvinyl chloride by emulsion and microsuspension polymerization processes.
• the splitting of the fatty oil can be carried out as follows: the fatty oil is reacted with water at a temperature in the range of 150° to 250° C., preferably about 185° to 215° C., under a pressure of from 15 to 50 bar, preferably 20 to 35 bar. After 5 or 6 hours the glycerol/water phase is separated and the above procedure preferably repeated twice to improve the yield. After the last separation of the glycerol/water phase, the resulting fatty acid mixture is distilled under reduced pressure.
• the conversion of the oleic fatty acid mixture into dihydrostearic acid can be carried out as follows.
• the fatty acid mixture is mixed with acetic acid and sulfuric acid, and the resulting mixture heated to a temperature in the range of from 50° to 90° C., preferably from 60° to 80° C., and treated with hydrogen peroxide to form 9,10-dihydroxystearic acid.
• the 9,10-dihydroxystearic acid is then directly converted into an alkali metal, ammonium or alkanolammonium salt thereof.
• the invention is illustrated but not limited by the following Example in which the emulsifiers prepared in accordance with the invention using fatty acids of the invention are compared with those obtained from a split tallow fatty acid in accordance with the prior art.
• the sunflower oil fatty acid prepared above had the following composition, as determined by gas chromatography:
• the Table shows that favorable results with respect to coagulate formation are obtained with the emulsifier soaps according to the invention, although these emulsifiers have a linoleic acid content of the same high order as emulsifiers obtained from split tallow fatty acid in accordance with the prior art.
• the 9,10-dihydroxystearic acid from the sunflower oil fatty acid of the invention and the 9,10-dihydroxystearic acid from split tallow fatty acid were prepared as follows:

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• Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Organic Chemistry (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Colloid Chemistry (AREA)
• Polymerisation Methods In General (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Detergent Compositions (AREA)

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Citations (17)

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• 1987
  • 1987-05-08 DE DE19873715421 patent/DE3715421A1/de not_active Withdrawn
• 1988
  • 1988-04-30 AT AT88106970T patent/ATE83491T1/de not_active IP Right Cessation
  • 1988-04-30 ES ES88106970T patent/ES2053614T3/es not_active Expired - Lifetime
  • 1988-04-30 EP EP88106970A patent/EP0293611B1/de not_active Expired - Lifetime
  • 1988-04-30 DE DE8888106970T patent/DE3876684D1/de not_active Expired - Fee Related
  • 1988-05-09 JP JP63113414A patent/JP2590198B2/ja not_active Expired - Lifetime
• 1992
  • 1992-10-01 US US07/955,393 patent/US5296576A/en not_active Expired - Fee Related
• 1993
  • 1993-01-11 GR GR930400016T patent/GR3006760T3/el unknown

Patent Citations (19)

Non-Patent Citations (8)

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